Process for removing acid components from hydrocarbon distillates



Patented Jan. 1940 r I a 2 UNITED {Para-m oFFrcs I r-access FOItl3 l ;\3;(ir ACID (Zlbn liilr I i t:

f mm'rs. mom urn, o

- LATES armou- DISTIL- David Louis rumba, Berkeley, cant, aulgnor to I 7 J Shell PDevelopment Company, Calif.,;a corporation of Delaware No Drawing.

' T 'hisinvention is'a continuation-in partof;my-

co-pending applications Serial Nos. 102,892 and 102,893, filed septemberfzsgraas; and, deals with xiR-iYRzxz, in. which the removal of weakly acid reacting'organic sub- -tions of causticalkali containing'a solubility promoter for these substances, 'and'more particularly of mercaptans from deals with -the removal, 10 hydrocarbon distillates. It is frequen necessary to eliminatejsmall quantities of ur ent relatively weak acid-reacty a :Kdipropylene 'glycols) or analogous amino hy- Ving components suchias mercaptans, phenols,

, thiophenols, alkylphenols, fatty acid'sletcgirom their solutions in neutral or weakly basic reacting organic liquids which are substantially immiscible;- 1

with water such as the liquid hydrocarbonsderived from petroleum, benzene tohiene; xylene,-,

substituted normally liq d hydrocarbons which are'substantially insoluble in water, for instance,

chlorinated hydrocarbons, of which chlorethane, ethylene dichloride,' 'trichlorethylene, carbontetrachloride, chlorpropane, chlorbutylene, chlorbenzene, brombenzene, are examples; or nitro-v 1 gen containing hydrocarbons; lsuchas ampl or higher amines, aniline, water-insoluble pyridine derivatives, petroleum bases, etc. a In order that the water-insoluble organic liquids may be treated by my process, they must be substantially inert and resistant to chemical reaction with, strong, aqueous alkali when contacted therewith for of time, e.g., about temperatures. 7, s a My invention comprises extracting organic acids which are difficult to extract, such as the weak acids having dissociation constants lower than those of fatty acids, e.g., niercaptans, phenols, etc., contained in water insoluble oro ganic liquids which are substantially inert toward strong aqueous caustic alkali solutions at normal room temperature, with an aqueous solution of caustic alkali in which is dissolved a substantial amount of a solubility promoter for. weak organic acids, under conditions to absorb at least a major ortionof the weak organic acidsin the aqueous a ethylene glycol containing 10 and 15% water, re-

solution, and to form two layers and separating the layersv In the applica ions Serial Nos.

102,892 and that certain .p'olar substances which are at least partly miscible with aqueous solutions of strong caustic alkali, promote the solvent power for weak organic acids of aqueous caustic alkali'solutions in which they are dissolved. I have shown that among other comp'ounds, certainglycols intotal number of carbon atoms of 4 "oustojthe above ether's." I

If ,the'totalnurnber oiicarbon atoms in the alkaline radicals exceeds unsuitedffor thy-purpose, becauseithey are insufficiently soluble in strong aqueous caustic alkali ation of the spent aqueous solutions of caustic short periods 1Q minutes or less at room important I a cause the described ethers having 6 or less carbon 7 1 atoms are substantially insoluble in hydrocarbon 7 oils in the-presence 102,893, filed September 28,1936, I have disclosed etc.,

San Francisco,

Application February '1, 19:9, I

1 covered that of the many glycols, amino alcohols and sdiamines, those having the iormula hydroxyradicals, Y is an'oxyge'n or sulfur atom 'ahd Ri [and R1 are alkyiene-radicais' having a to 6. Typical examples of thesecompounds are dihydroxy diethyl ether (diethylene glycol), beta hydroxy beta amino "diethylpether, beta-beta.

diamino diethyl ether; beta-beta or beta-gamma or gamma-gamma dihydroxy' dipropyl ethers droxy or diamino compounds; thioethers analog- 6, the compounds are solutions and are excessively insoluble organic liquids; a Concentrations of the ethers in the'aqueous solution should preferably be kept between the soluble in water- X: are amino, or

the beta-beta limits of about,25-75%. and the'amo'unt oi water in the solution should'be not less than1'5'% and 750%, If lessjthan"15% water is used, 'regenere tainina absorb'ed 7 weak organic acids, by "steam stripping is very difllcult, if not impossible. Qn the other, hand, the presence of more than l5 not more 'than 70% and preferably-not more than a alkaline solution con water does not cause excessive hydrolysiswith consequent reduction of extraction power for the weak organic acids, asrwhad been believed by earlier investigators, hydrolysisbeing primarily a function of the alkalinity of the solution. More-' over, to minimize'losses of the ethers due to their being: dissolv in the organic water-insoluble liquid, it may be desirable to use 15%;or more water. However, this last consideration is unwhentreating hydrocarbon oils besmaller than 15%; For example, when treating isooctane with 20 volume percent or, aqueous dispectively, separating the liquids and analyzing glycol' was found dissolved in of amounts of water muchcedure being such that less than .01% diethylene glycol would have been detected. v e The effect of some of the compounds of my invention on the extraction emciency oi aqueous caustic alkali is illustrated by the following examples:

' A solution of normal 'arnyl mercaptan in gasoline was treated with aqueous solutions of sodium hydroxide containingvarious solubility promoters, and the distribution constants K for the mercaptan were determined, K being concentration of mercaptan in aqueous phase concentration of mercaptan in oil phase Results were as follows:

Concentra- Solubility promoter tioiingig'o- 22 6 K Percent None I 3. 84 .l. 25 None.-. 5. 0 1. 03 Dlcthylene glycol 50 5.0 Beta-beta dihydroxy diethyl I ether 5. 0 20 Beta-beta diamino diethyl ether. 25. 3. 84 26 Beta amino beta hydroxy diethyl ether 50 5. 0 257, Dipropylene glycol 50 6. 0 237 Aqueous solutions of various causticalkalis may be used. The alkali metal hydroxides are most useful and eifective, although ammonia, alkaline earth hydroxides, quaternary ammonium bases, alkali metal carbonates, etc., may also be suitable.

The concentration of the aqueous'caustic alkali may vary within wide limits. In general, we prefer to use caustic alkali solutions which are above about 2 normal and preferably between 4 to 10 normal, calculated onthe totalsolution, although higher and lower concentrations may be used. 1

The temperature of the extraction is preferably kept between 0 and C., the extraction efficiency decreasing with increases in the temperature; and at temperatures below about 0 C. difliculties are frequently encountered due to precipitation of a portion of the solubility promoter and/or excessive viscosity of the aqueous caustic alkali containing the solubility promoter.

The extraction of the organic acids from their solutions in the organic liquids described before may be carried out by simply mixing the solution with a predetermined amount of the aqueous caustic alkali solution in which is dissolved a substantial amount of the solubility promoter, and then separating the liquids. The resulting aqueous solution contains most of the solubility promotor and the major portion of the organic acids, while the organic liquid stripped from the acids contains a trace of solubility promoter. By washing the stripped organic liquid with water, the

solubility promoter is re-extracteci by the latter.

The aqueous solution so obtained may then be added to the caustic alkali solution containingthe bulk of the solubility promoter and excess water may be separated from the resulting solution by distillation.

More thorough extraction may be had, however,

in a multi-stage countercurrent extraction system or in a packed tower.

The amount of aqueous caustic alkali solution required in the extraction is normally above about 5% by volume and for economical reasons seldom exceeds about 100% by volume. Normal-= ly from about 10 to 50%. by volume is used depending upon the required thoroughness of removing the weak organic acids.

Spent aqueous. caustic alkali solution containing the solubility promoter and weak organic acids may be regenerated by distillation, steaming and/or oxidation, according to well-known principles.

The following example further illustrates my invention:

A .West Texas straight run full range gasoline containing .0699% of mercaptan sulfur was exline. was then treated under identical conditions 7 with a 5N aqueous caustic soda solution containing 50% beta hydroxy betaf amino diethyl ether.

58.7% ,of the mercaptan sulfur was removed.

I claim as my invention: I

1. In the process of separating organic acid reacting substances contained in a water-insoluble neutral or basic organic liquid, the steps comprising treating said liquid with an aqueous solution of a strong base containing a substantial amount of a dissolved compound having the formula x1RiYR2X2, in which R1 and R2 are alkylene radicals having a total number of carbon atoms from 4 to 6, X1 and X: are radicals selected from the group consisting of amino and hydroxy radicals, and Y is an element selected from the group 7 consisting of oxygen or sulfur, said solution containing from 15 to water, under conditions to absorb at least a portion of said acid reacting substances in said aqueous solution and to form two liquid layers, one comprising the aqueous solution containing absorbed acid reacting substances, and the other consisting essentially of the treated organic liquid and separating the layers.

2. The process of claim 1 in which the aqueous base solution contains between 25 and of the compound.

3. The process of claim 1 in which the aqueous base is from 2 to 10 normal.

4.-The process of claim 1 in which the organic liquid is extracted with 5 to volume percent of aqueous base solution containing the compound.

5. The process of claim 1 in which the base is an alkali metal hydroxide.

6. The process of claim 1 in which the compound is diethylene glycol. 1

7. The process of claim 1 in which the compound is dipropylene glycol.

8. The process of claim 1 in which the compound is beta amino beta hydroxy diethyl ether.

9. In the process of separating mercaptans from hydrocarbon distlllates containing some by extraction with an aqueous solution of a strong base, the improvement comprising extracting said distillate with at least 5 volume per cent of a 2 to 10 normal aqueous alkali metal hydroxide solution in which is dissolved between 25 and 75% of a dissolved compound having the formula X1R1YR2X2, in which R1 and R2 are alkylene radicals having a total number of carbon atoms from 4 to 6, X1 and X: are radicals selected from the group consisting of amino and hydroxy radicals, and Y is an element selected from the group consisting of oxygen or sulfur, said solution containing from 15 to 70% water, under conditions to absorb at least a major portion of the mercaptans in the. aqueous solution and to form two liquid layers, one comprising the aqueous alkali metal hydroxide solution containing substantially all of the compound and the major portion of the mercaptans, and the other consisting essentially of treated hydrocarbon distillate, and separating the layers. V

. DAVIDLOUIS YABROFF 

